EP0810902B1 - Vorrichtung und ihre verwendung zur oxichlorierung - Google Patents
Vorrichtung und ihre verwendung zur oxichlorierung Download PDFInfo
- Publication number
- EP0810902B1 EP0810902B1 EP95924203A EP95924203A EP0810902B1 EP 0810902 B1 EP0810902 B1 EP 0810902B1 EP 95924203 A EP95924203 A EP 95924203A EP 95924203 A EP95924203 A EP 95924203A EP 0810902 B1 EP0810902 B1 EP 0810902B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tubes
- nozzles
- catalyst
- gas
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005660 chlorination reaction Methods 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- QYAMPIKBANGIEM-UHFFFAOYSA-N chloroethene;hydrochloride Chemical compound Cl.ClC=C QYAMPIKBANGIEM-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—Coils
Definitions
- Oxichlorination is the conversion of ethylene with hydrogen chloride and oxygen or one understood oxygen-containing gas, where 1,2-dichloroethane (EDC) is formed.
- EDC 1,2-dichloroethane
- hydrogen chloride is usually the thermal Cleavage from EDC to vinyl chloride Hydrogen chloride used.
- Catalysts used on dust-fine supports such as alumina, metal halides, preferably Copper chloride.
- the catalyst particles have here an average diameter of about 50 microns and form a fluidized bed that either only from the Reaction gas streams, optionally with Portions of inert gas, or additionally from one Recycle gas flow is carried. With this procedure the heat of reaction is distributed in the fluidized bed and on Cooling surfaces dissipated, creating an even Temperature distribution in the fluidized bed reactor is reached.
- the catalyst particles have a high Have abrasion resistance. This property is used in given essentially by the carrier material for what in addition to the alumina already mentioned Silicic acid, diatomaceous earth or pumice stone used will.
- EP-A-0 446 379 discloses a reactor for production ⁇ - ⁇ -unsaturated nitriles known in the lower part a horizontally arranged gas supply for an olefin or tertiary butyl alcohol is provided, wherein at the Bottom of the gas supply a variety of nozzles is arranged, as well as a further feed for a Oxygen containing gas that is below and parallel to the other gas supply is arranged, the distance between the two gas feeds is 25 to 300 mm. A too short distance can damage the Gas supplies by melting due to a cause unusual reaction while at too long Distances the olefin or the tertiary Butyl alcohol is insufficient with the oxygen containing gas is mixed, which is the yield of nitrile decreased.
- GB-A-1 265 770 describes a reactor for Fluid bed reactions with a distributor plate in the lower one Part of the reactor known, under which a gas supply and in the edge area of the reactor housing above and adjacent another gas supply to the distributor plate is provided. This further gas supply causes the catalyst does not settle in the edge area. This Precautions serve in particular to ensure that the catalyst is not reduced.
- One can be inside the fluidized bed further gas supply can be provided in the lower part the reactor is arranged so that good mixing the reactants occur at the base of the fluid bed.
- WO 94/19099 is a device for oxychlorination known, which is characterized by a reactor 1, a lower limit 2 for a fluidized bed catalyst 3, a gas inlet (manifold) 4, contains the nozzles 5, the nozzles 5 in tubes 6 flow into a horizontal flow Impart component in the flow direction, and a Gas inlet 9 below the limit 2.
- Preferred embodiments are directed to the fact that the pipes mentioned, into which the nozzles open, at the end Steering devices with outlet openings included, or that these tubes slant up or in point horizontally or diagonally downwards and these tubes end freely in the catalyst bed, or that these pipes or the outlet openings Adjacent pipes are arranged so that the escaping gas jets not frontally meet and / or not an adjacent pipe to meet.
- Direct other preferred embodiments insisted that by limiting pipes are passed in which nozzles below the Limit, but above the lower end of the performed pipes are arranged, wherein preferably these nozzles below half the length of the relevant pipes are attached, especially in the Distance from about a diameter of the tube lower end.
- the device according to the invention is advantageous in this way designed that the number of tubes 8 the same Number of tubes 6 evenly over the cross section a reactor 1 is arranged distributed opposite.
- aligning one of the tubes 8 and 6 is an assignment of the amounts of gases reacting with one another given from tubes 8 and 6 to a particular extent.
- Device are an equal number of Pipes 8 and 6 offset from each other. This geometry causes the lowest possible erosion of the pipes 6 by the gas stream rising from the tubes 8. Furthermore, with this arrangement one can achieve that of pipes 8 and 6 into the catalyst fluidized bed 3 reactants occurring immediately an intimate contact exposed to the catalyst. This will make the desired reaction towards EDC formation favors and side reactions, such as the Combustion of ethylene with oxygen, pushed back.
- the number of tubes is 6 of the number of tubes 8 different. But here too the important thing is distribution of these pipes as evenly as possible over the Cross section of the reactor 1. This shape gives the Possibility to increase the number of tubes 6 in one to change the existing reactor without at the same time Adapt pipes 8, which means a lot of effort would.
- FIG. 1 An apparatus according to FIG. 1 is used.
- a reactor 1 2.8 m in diameter and 26 m in height the reactants preheated to 160 ° C become gaseous initiated.
- a mixture of 5974 kg / h Hydrogen chloride and 1417 kg / h oxygen flow through the gas inlet 4 via the nozzles 5 and the pipes 6 in the fluidized catalyst bed 3.
- the nozzles 5 have different diameters so that one is possible uniform gas distribution to all nozzles 5 and thus is achieved over the cross section of the reactor 1.
- the diameter of the nozzles 5 increases downstream the gas inlet 4 from 8.6 mm to 9.3 mm and further to 10 mm along the various pressure drops the gas inlet up to the respective nozzles 5 compensate.
- the tubes 6 with an inner diameter of 40 mm have a length of 300 mm. 2380 kg / h Ethylene flow through the gas inlet 7 and Pipes 8 with the nozzles 9 through the lower limit 2.
- reactor 1 is a catalyst Copper (II) chloride on an alumina support in in the form of a fluidized catalyst bed 3.
- the above reactants become fluidized beds introduced. Flows to fluidize the fluidized bed additionally a circulating gas flow of 8780 kg / h over the Gas inlet 7 and the pipes 8 through the lower Limitation 2 in the reactor 1.
- the top ends of the Pipes 8 are flush with the lower limit 2.
- the Distance between this lower limit and the lower ends of the tubes 6 is 400 mm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19505664 | 1995-02-20 | ||
DE19505664A DE19505664C2 (de) | 1995-02-20 | 1995-02-20 | Vorrichtung und ihre Verwendung zur Oxichlorierung |
PCT/EP1995/001874 WO1996026003A1 (de) | 1995-02-20 | 1995-05-17 | Vorrichtung und ihre verwendung zur oxichlorierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0810902A1 EP0810902A1 (de) | 1997-12-10 |
EP0810902B1 true EP0810902B1 (de) | 1998-10-21 |
Family
ID=7754432
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95924203A Expired - Lifetime EP0810902B1 (de) | 1995-02-20 | 1995-05-17 | Vorrichtung und ihre verwendung zur oxichlorierung |
Country Status (21)
Country | Link |
---|---|
EP (1) | EP0810902B1 (no) |
JP (1) | JPH11500062A (no) |
KR (1) | KR100368512B1 (no) |
CN (1) | CN1089026C (no) |
AU (1) | AU702305B2 (no) |
BG (1) | BG62436B1 (no) |
BR (1) | BR9510383A (no) |
CA (1) | CA2213446C (no) |
CZ (1) | CZ289342B6 (no) |
DE (2) | DE19505664C2 (no) |
ES (1) | ES2126296T3 (no) |
HU (1) | HU221883B1 (no) |
IN (1) | IN188066B (no) |
NO (1) | NO973714D0 (no) |
PL (1) | PL180784B1 (no) |
RO (1) | RO118119B1 (no) |
RU (1) | RU2157726C2 (no) |
SK (1) | SK282850B6 (no) |
UA (1) | UA42056C2 (no) |
WO (1) | WO1996026003A1 (no) |
ZA (1) | ZA961278B (no) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19753165B4 (de) | 1997-12-01 | 2006-10-19 | Vinnolit Monomer Gmbh & Co. Kg | Verfahren zur Herstellung von 1,2-Dichlorethan durch Oxichlorierung |
DE19849709C2 (de) * | 1998-10-28 | 2000-09-14 | Krupp Uhde Gmbh | Verfahren und Wirbelschicht-Reaktor zur Oxichlorierung von Ethylen, Sauerstoff und HCl |
DE19903335A1 (de) * | 1999-01-28 | 2000-08-17 | Vinnolit Monomer Gmbh & Co Kg | Verfahren für die Herstellung von 1,2-Dichlorethan aus der Oxichlorierung |
DE19911078A1 (de) * | 1999-03-12 | 2000-09-21 | Krupp Uhde Gmbh | Verfahren zur Herstellung von VCM |
US6991767B1 (en) * | 2000-09-18 | 2006-01-31 | Procedyne Corp. | Fluidized bed gas distributor system for elevated temperature operation |
DE10258180A1 (de) * | 2002-12-12 | 2004-06-24 | Basf Ag | Verfahren zur Herstellung von Chlor durch Gasphasenoxidation von Chlorwasserstoff |
JP2007503463A (ja) * | 2003-05-09 | 2007-02-22 | ザ・スタンダード・オイル・カンパニー | ガスクーラーを有する流動床反応器 |
US7488601B2 (en) | 2003-06-20 | 2009-02-10 | Roche Diagnostic Operations, Inc. | System and method for determining an abused sensor during analyte measurement |
MY140160A (en) | 2004-01-28 | 2009-11-30 | Shell Int Research | Heat exchanger for carrying out an exothermic reaction |
CA2558823A1 (en) * | 2004-03-08 | 2005-09-15 | Shell Internationale Research Maatschappij B.V. | Gas distributor for a reactor |
US8221674B2 (en) * | 2005-12-23 | 2012-07-17 | Siemens Vai Metals Technologies Gmbh | Distributor base |
CN100435928C (zh) * | 2006-09-20 | 2008-11-26 | 浙江大学 | 一种气体分布器 |
DE102006049546A1 (de) * | 2006-10-20 | 2008-04-30 | Vinnolit Gmbh & Co.Kg Profitcenter Vintec | Vorrichtung und Verfahren zur Oxichlorierung |
DE102008048526A1 (de) * | 2008-09-23 | 2010-04-01 | Uhde Gmbh | Verfahren zur Nutzung der im Herstellungsprozess von 1,2-Dichlorethan aus Ethylen in einem Wirbelschichtreaktor anfallenden Reaktionswärme |
US8092755B2 (en) * | 2009-04-06 | 2012-01-10 | Lummus Technology Inc. | Devices for injection of gaseous streams into a bed of fluidized solids |
US20150064089A1 (en) * | 2013-08-29 | 2015-03-05 | Honeywell International Inc. | Fluidized bed reactors including conical gas distributors and related methods of fluorination |
CN104941524B (zh) * | 2014-03-31 | 2020-11-03 | 英尼奥斯欧洲股份公司 | 用于氨氧化反应器的进料分布器设计 |
CN105727846B (zh) * | 2016-01-29 | 2019-02-05 | 清华大学 | 导流式喷动床和导流式喷动流化床 |
JP6373523B1 (ja) * | 2017-06-19 | 2018-08-15 | 旭化成株式会社 | 化合物の製造方法 |
US20230026757A1 (en) * | 2019-11-20 | 2023-01-26 | China Petroleum & Chemical Corporation | Gas Distribution Plate, Fluidizing Device and Reaction Method |
KR20230076022A (ko) * | 2021-11-23 | 2023-05-31 | 주식회사 엘지화학 | 기포탑 반응기 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1265770A (no) * | 1969-07-01 | 1972-03-08 | ||
US4436507A (en) * | 1981-07-16 | 1984-03-13 | Foster Wheeler Energy Corporation | Fluidized bed reactor utilizing zonal fluidization and anti-mounding air distributors |
US4801731A (en) * | 1987-12-14 | 1989-01-31 | E. I. Du Pont De Nemours And Company | Preparation of acrylonitrile |
CA2042584C (en) * | 1989-10-04 | 1993-11-09 | Hiroaki Muroya | .alpha., .beta.-unsaturated nitrile manufacturing apparatus |
DE9116161U1 (de) * | 1991-12-07 | 1992-03-26 | Hoechst Ag, 65929 Frankfurt | Vorrichtung zur Herstellung von 1,2-Dichlorethan durch Oxichlorierung |
DE4305001A1 (de) * | 1993-02-18 | 1994-08-25 | Hoechst Ag | Vorrichtung zur Oxichlorierung |
-
1995
- 1995-02-20 DE DE19505664A patent/DE19505664C2/de not_active Expired - Fee Related
- 1995-05-17 KR KR1019970705738A patent/KR100368512B1/ko not_active IP Right Cessation
- 1995-05-17 WO PCT/EP1995/001874 patent/WO1996026003A1/de active IP Right Grant
- 1995-05-17 EP EP95924203A patent/EP0810902B1/de not_active Expired - Lifetime
- 1995-05-17 AU AU28810/95A patent/AU702305B2/en not_active Ceased
- 1995-05-17 HU HU9801625A patent/HU221883B1/hu not_active IP Right Cessation
- 1995-05-17 CN CN95197689A patent/CN1089026C/zh not_active Expired - Fee Related
- 1995-05-17 CA CA002213446A patent/CA2213446C/en not_active Expired - Fee Related
- 1995-05-17 DE DE59504023T patent/DE59504023D1/de not_active Expired - Fee Related
- 1995-05-17 RO RO97-01537A patent/RO118119B1/ro unknown
- 1995-05-17 JP JP8525326A patent/JPH11500062A/ja not_active Ceased
- 1995-05-17 SK SK1134-97A patent/SK282850B6/sk unknown
- 1995-05-17 BR BR9510383A patent/BR9510383A/pt not_active IP Right Cessation
- 1995-05-17 CZ CZ19972657A patent/CZ289342B6/cs not_active IP Right Cessation
- 1995-05-17 RU RU97116001/12A patent/RU2157726C2/ru not_active IP Right Cessation
- 1995-05-17 UA UA97094673A patent/UA42056C2/uk unknown
- 1995-05-17 PL PL95321830A patent/PL180784B1/pl unknown
- 1995-05-17 ES ES95924203T patent/ES2126296T3/es not_active Expired - Lifetime
-
1996
- 1996-01-29 IN IN143CA1996 patent/IN188066B/en unknown
- 1996-02-19 ZA ZA961278A patent/ZA961278B/xx unknown
-
1997
- 1997-07-04 BG BG101745A patent/BG62436B1/bg unknown
- 1997-08-12 NO NO973714A patent/NO973714D0/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
KR19980702341A (ko) | 1998-07-15 |
MX9706276A (es) | 1997-11-29 |
EP0810902A1 (de) | 1997-12-10 |
HU221883B1 (hu) | 2003-02-28 |
CZ265797A3 (cs) | 1998-02-18 |
CZ289342B6 (cs) | 2002-01-16 |
PL321830A1 (en) | 1997-12-22 |
DE19505664C2 (de) | 1996-12-12 |
ES2126296T3 (es) | 1999-03-16 |
SK113497A3 (en) | 1998-01-14 |
DE19505664A1 (de) | 1996-08-29 |
BG62436B1 (bg) | 1999-11-30 |
AU2881095A (en) | 1996-09-11 |
HUT77918A (hu) | 1998-10-28 |
AU702305B2 (en) | 1999-02-18 |
PL180784B1 (pl) | 2001-04-30 |
CN1089026C (zh) | 2002-08-14 |
CA2213446C (en) | 2002-01-29 |
IN188066B (no) | 2002-08-17 |
RU2157726C2 (ru) | 2000-10-20 |
UA42056C2 (uk) | 2001-10-15 |
CN1175219A (zh) | 1998-03-04 |
NO973714L (no) | 1997-08-12 |
ZA961278B (en) | 1996-08-27 |
RO118119B1 (ro) | 2003-02-28 |
CA2213446A1 (en) | 1996-08-29 |
SK282850B6 (sk) | 2002-12-03 |
BR9510383A (pt) | 1998-06-02 |
NO973714D0 (no) | 1997-08-12 |
DE59504023D1 (de) | 1998-11-26 |
WO1996026003A1 (de) | 1996-08-29 |
JPH11500062A (ja) | 1999-01-06 |
BG101745A (en) | 1998-05-29 |
KR100368512B1 (ko) | 2003-03-26 |
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